Optically active styrene compounds

ABSTRACT

Optically active compounds of the formula I ##STR1## in which R 1  is C 1  -C 4  -alkyl, phenyl or benzyl, R 2  is a radical of the formula II or IIa ##STR2## in which R 3  is H or --CH 3 , or R 1  and R 2  together form a radical of the formula ##STR3## in which R 2  has the meaning given above; and * represents predominantly R or predominantly S configuration. 
     The compounds can be polymerized to give homopolymers or copolymers. The compounds and the polymers can be complexed with iridium(I) salts in the presence of a diene. The complexes are suitable as enantioselective catalysts.

This is a divisional of application Ser. No. 258,369 filed on Oct. 17,1988, now U.S. Pat. No. 4,904,790, which is a divisional of Ser. No.047,099 filed on May 8, 1987, now U.S. Pat. No. 4,800,224 issued on Jan.24, 1989.

The invention relates to optically active styrene derivatives having a2-pyridinaldimino group or 2-(aminomethyl)-pyridine group, their homo-and copolymers with olefinic comonomers, complexes of the monomers andpolymers with iridium(I), and their use as enantioselective catalystsfor the transfer hydrogenation of prochiral ketones with secondaryalcohols.

P. Hodge et al., in Polymer-supported Reactions in Organic Synthesis,John Wiley & Sons (1980), pages 281-283, describe polymer-bonded rhodiumcomplexes of2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphinobutane)(DIOP) as enantioselective catalysts for hydrogenations.

K. Ohkubo et al. in Inorg. Nucl. Chem. Letters, Vol 17, pages 215-218(1981), describe amberlite-bonded rhodium complexes of DIOP, which aresuitable as enantioselective hydrogenation catalysts for prochiralketones.

G. Zassinovich et al., in Journal of Organometallic Chemistry, 222,pages 323-329 (1981), describe cationic iridium(I) complexes with a1,5-cyclooctadiene ligand and a 2-pyridinaldimine ligand which issubstituted at the imine N atom by optically active α-phenylethyl orpinane-3-methyl. They act as enantioselective homogeneous catalysts inthe transfer hydrogenation of prochiral ketones with isopropanol.Although high yields are achieved in the reaction, the optical yield(enantiomeric excess) is relatively low.

The invention relates to optically active compounds of the formula I##STR4## in which R¹ is C₁ -C₄ -alkyl, phenyl or benzyl, R² is a radicalof the formula II or IIa ##STR5## in which R³ is H or --CH₃, or R¹ andR² together form a radical of the formula ##STR6## in which R² has theabovementioned meaning and * represents predominantly the R orpredominantly the S configuration.

C₁ -C₄ -alkyl radicals R¹ may be branched alkyl but are preferablylinear alkyl. Examples are methyl, ethyl, n-propyl, i-propyl, n-, i- andt-butyl. R¹ is preferably methyl or benzyl.

The compounds of the formula I are obtainable, for example, by reactinga pyridinealdehyde of the formula III ##STR7## with an amine of theformula IV ##STR8## or with an amine of the formula V ##STR9## toprepare the compounds for the formula I in which R² is a radical of theformula II, and hydrogenating the resulting pyridinaldemines with LiAlH₄to prepare compounds of the formula I in which R² is a radical of theformula IIa, R¹ and R³ having the abovementioned meaning.

The reaction is advantageously carried out in a solvent and preferablyat elevated temperature, in particular at 40°-120° C. Suitable solventsare, for example, hydrocarbons (for example, pentane, hexane,cyclohexane, methylcyclohexane, benzene, toluene and xylene),halohydrocarbons (for example, chloroform, methylene chloride, carbontetrachloride and 1,1,2,2-tetrachloroethane), ethers (for example,diethyl ether, dioxane and tetrahydrofuran) and alcohols (for example,methanol, ethanol and n-propanol). Advantageously, the solvents used arethose with which the resulting water of reaction can be removed from thereaction medium by azeotropic distillation. The desired compounds areadvantageously isolated by distillation or crystallization. The reactionof the resulting imines of the formula I, in which R² is a radical ofthe formula II, with LiAlH₄ to prepare the amines for the formula I, inwhich R² is a radical of the formula IIa, is advantageously carried outin a manner known per se, at a temperature of, preferably, -20° to 30°C. in an ether (for example, diethyl ether, dioxane or tetrahydrofuran).To isolate the desired compounds, the reaction mixture is hydrolysed,and the organic phase is separated off and then chromatographed ordistilled.

The pyridinealdehydes of the formula III are known and are commerciallyavailable.

The novel compounds of the formula IV in which R¹ is C₁ -C₄ -alkyl,phenyl or benzyl are obtainable by the process described in G. Wulff etal., Makromol. Chem. 183, pages 2459-2467 (1982). It has been found thatthe optical rotation of the (R)- and (S)-1-(4-vinylphenyl)ethylaminesstated there is too small, and consequently mixtures with an excess ofone stereoisomeric amine in each case are disclosed. The values of theoptical rotation for the pure stereoisomers are about 12° higher in eachcase. The starting materials of the formula ##STR10## which are requiredfor the process described by G. Wulff et al. are obtained by the processdue to E. L. Foreman in JACS 62, page 1436 (1940). A traditional methodof separating racemic reaction products as salts of the purestereoisomers with optically active organic acids by fractionalcrystallization leads to the optically pure amines having an R or Sconfiguration.

The novel amine of the formula V is obtained by a process analogous tothe process described by K. Weinges et al. in Chem. Ber. 113, pages710-721 (1980), by reaction of(+)-2-amino-1-phenyl-1,3-propandiol-hydrobromide with p-styrylaldehyde.

The invention furthermore relates to pure stereoisomeric opticallyactive amines of the formulae IV or V ##STR11## in which R¹ is C₁ -C₄-alkyl, phenyl or benzyl and the chiral * C atom in formula IV haseither the R or the S configuration, and the chiral C atoms in formula Vhave the 2R, 4S, 5S configuration. The compounds of the formula I aresuitable as N,N-chelate ligands for the preparation of complexes.

The invention furthermore relates to iridium complexes with compounds ofthe formula I, wherein the complex corresponds to the formula VI or VIa##STR12## in which * represents predominantly R or predominantly Sconfiguration, R¹ and R³ have the meaning given above, R⁴ and R⁵ areeach H or together form a bond, X⁻ is an anion of a monobasic inorganicor organic acid and Y is an open-chain or cyclic diene having 6 to 10 Catoms, whose diene groups are bonded via 1 or 2 C atoms. The compoundsof the formulae VI and VIa can also be in the hydrated form.

R¹ in formula VI is preferably methyl or benzyl.

The anion X.sup.⊖ of a monobasic inorganic or organic acid may be, forexample, F.sup.⊖, Cl.sup.⊖, Br.sup.⊖, I.sup.⊖, ClO₄ ⊖, NO₃ ⊖, BrO₃ ⊖,HSO₄ ⊖, H₂ PO₃ ⊖, H₂ PO₄ ⊖, BF₄ ⊖, B(phenyl)₄ ⊖, PF₆ ⊖, SbF₆ ⊖, AsF₆ ⊖,SbCl₆ ⊖, SbCl₅ F.sup.⊖, HCOO.sup.⊖, CH₃ COO.sup.⊖, CCl₃ COO.sup.⊖, CF₃COO.sup.⊖, CH₃ SO₃ ⊖, CCl₃ SO₃ ⊖, CF₃ SO₃ ⊖, phenyl-SO₃ ⊖ orp-toluyl-SO₃ ⊖. In a preferred embodiment, X.sup.⊖ is halide, BF₄ ⊖,ClO₄ ⊖, CF₃ SO₃ ⊖ or PF₆ ⊖.

A preferred subgroup of iridium complexes comprises those in whichX.sup.⊖ in the formulae VI and VIa are Cl.sup.⊖, Br.sup.⊖, I.sup.⊖, BF₄⊖, ClO₄ ⊖, CF₃ SO₃ ⊖ or PF₆ ⊖, and R⁴ and R⁵ together form a bond.

Another preferred subgroup of iridium complexes comprises those in whichX⁻ in the formulae VI and VIa are BF₄ -, ClO₄ -, CF₃ SO₃ - or PF₆ - andR⁴ and R⁵ are each H.

Y is preferably a diene having 6 to 8 C atoms, whose diene groups arebonded, in particular, via 2 C atoms. In a preferred embodiment, Y is1,5-cyclooctadiene, norbornadiene or 1,5-hexadiene.

Particularly preferred iridium complexes are those of the formulae##STR13## in which * represents predominantly R or predominantly Sconfiguration or 2R, 4S, 5S configuration.

The iridium complexes of the formula VI or VIa can be obtained byprocesses which are known per se [cf. Inorganica Chimica Acta 73 (1983),pages 275-279], by reacting [(acetonitrile)₂ (Y)]IrX, in which X and Yhave the meaning given above, with a compound of the formula I. Thepreparation of the acetonitrile complex is also described there. Thecomplexes [IrCl(Y)]₂ used for the preparation of the acetonitrilecomplex are obtainable, for example, by reactingdichlorotetrakis(alkene)diiridium(I) (alkene: for example cyclooctene)with a diene Y. The iridium complexes of the formulae VI and VIa canalso be obtained by processes which are known per se [cf. J. of Organom.Chem., 222, pages 323-329 (1981)], by reacting a diiridium complex ofthe formula [Ir(Y)Cl]₂ with a compound of the formula I.

The reactions are carried out in general at temperatures of -10° to 30°C. in an inert solvent and in the absence of air (inert gas atmosphere).Suitable inert solvents are, for example, hydrocarbons, such as benzene,toluene, xylene, petroleum ether, hexane, cyclohexane ormethylcyclohexane; and ethers, such as, for example, diethyl ether,dibutyl ether, tetrahydrofuran and dioxane, as well as halogenatedhydrocarbons, for example chloroform, methylene chloride andchlorobenzene. To prepare salts of the formula VI or VIa having anionsof monobasic inorganic or organic acids, the salts, in particular thechlorides, of the formula VI or VIa, can be subjected to doubledecomposition with an alkali metal salt M.sup.⊕ X'.sup.⊖ either directlyafter the reaction or after isolation and purification and redissolutionin polar solvents (for example alcohols, ethers or ketones, with orwithout the addition of water), and then isolated. X'.sup.⊖ is an anionof a monobasic inorganic or organic acid and differs from X.sup.⊖, andM.sup.⊕ is preferably sodium.

The compounds of the formula I are suitable for the preparation ofpolymers having optically active side groups. The invention furthermorerelates to homopolymers and copolymers having optically active sidegroups, and containing, relative to the polymers,

(a) 0.005 to 100 mol % of at least one repeating structural element ofthe formula VII ##STR14## in which R¹ is C₁ -C₄ -alkyl, phenyl orbenzyl, R² is a radical of the formula II or IIa ##STR15## in which R³is H or --CH₃, or R¹ and R² together form a radical of the formula##STR16## in which R² has the meaning given above; and * representspredominantly R or predominantly S configuration, and

(b) 99.995 to 0 mol % of at least one structural element which isderived from an olefinic comonomer and differs from component (a).

The preferences which apply to the structural elements of the formulaVII are the same as those which apply to the compounds of the formula I.The structural elements of the formula VII are preferably contained inan amount of 0.05 to 100, in particular 0.1 to 50, especially 0.1 to 10mol %, and the structural elements of an olefinic comonomer areaccordingly contained in an amount of 99.95 to 0, in particular 50 to99.9, especially 99.9 to 90 mol %.

The structural element of the olefinic comonomer preferably correspondsto the formula VIII ##STR17## in which X¹ is hydrogen, X² is hydrogen,chlorine or methyl and X³ is hydrogen, methyl, chlorine, --CN or --CONR⁷R⁸, in which R⁷ and R⁸ independently of one another are H or C₁ -C₁₈-alkyl, or is phenyl, methylphenyl, methoxyphenyl, cyclohexyl,--COO--alkyl having 1-12 C atoms in the alkyl moiety, --COO--phenyl,--COO--alkyl-OH having 2-6 C atoms in the alkyl moiety, --OCO--alkylhaving 1-4 C atoms in the alkyl moiety, --OCO--phenyl, alkoxy having1-20 C atoms or phenoxy, or X² is hydrogen and X¹ and X³ together form agroup --CO--NR⁶ --CO-- or are each --COO--alkyl having 1-6 C atoms inthe alkyl moiety, R⁶ being straight-chain or branched C₁ -C₁₈ -alkyl,cyclohexyl or phenyl which can be monosubstituted or disubstituted by C₁-C₆ -alkyl, halogen, cyano, nitro and/or C₁ -C₃ -alkoxy.

Preferred copolymers are those in which, in formula VIII, X¹ is H, X² isH or --CH₃ and X³ is phenyl, cyclohexyl, --COO--alkyl having 1-12 Catoms in the alkyl moiety, --COO--hydroxyalkyl having 2 to 4 C atoms inthe alkyl moiety or --CONR⁷ R⁸, in which R⁷ and R⁸ independently of oneanother are H or C₁ -C₁₂ -alkyl.

Particularly preferred copolymers are those in which, in the formulaVIII, X¹ and X² are H and X³ is phenyl, or X¹ is H, X² is --CH₃ and X³is --COO--alkyl having 1 to 12 C atoms in the alkyl moiety.

Alkyl radicals X³, R⁶, R⁷ and R⁸ can be linear or branched andpreferably contain 1 to 12, in particular 1 to 6, C atoms. The polymersaccording to the invention can furthermore contain up to 60 mol %,relative to the monomers present, of structural elements of anolefinically diunsaturated or polyunsaturated crosslinking agent.Suitable polyunsaturated crosslinking agents are, for example,divinylbenzenes, divinyltoluenes, divinylnaphthalenes, divinylxylenes,divinylethylbenzenes, divinyl sebacate, trivinylbenzenes,trivinylnaphthalenes and polyvinylanthracenes; ethylene glycoldiacrylate, ethylene glycol dimethacrylate, N,N'-methylenediacrylamide,N,N'-methylenedimethylacrylamide, N,N'-ethylenediacrylamide, polyvinylethers of ethylene glycol, propanetriol, pentaerythritol and resorcinol.

The crosslinking agent is preferably used in an amount of 0.1-10 mol %.Preferred crosslinking agents are divinylbenzenes. By a suitable choiceof the comonomers and/or crosslinking agents, the properties of thepolymers can be adapted to the desired specific applications.

The polymers can have a mean molecular weight (M_(w)) of 1,000 to5,000,000, preferably 5,000 to 1,000,000, in particular 5,000 to 500,000(osmometric determination).

The polymers according to the invention can be obtained in a knownmanner, by polymerizing

(a) 0.005 to 100 mol % of at least one monomer of the formula I and

(b) 0 to 99.995 mol % of at least one olefinic comonomer which differsfrom component (a).

Free radical polymerization is preferred. About 0.01 to 5% by weight,preferably 0.01 to 1.5% by weight, relative to the total weight of themonomers and any crosslinking agents, of conventional free radicalinitiators, such as inorganic or organic peroxides or azo compounds, forexample hydrogen peroxide, potassium peroxydisulfate, tert-butylhydroperoxide, di-tert-butyl peroxide, peracetic acid, dibenzoylperoxide, diacyl peroxides, cumene hydroperoxide, tert-butylperbenzoate, tert-alkyl peroxydicarbonates and α,α'-azoisobutyronitrile,are advantageously used in the polymerization. The reaction temperaturesfor the free radical polymerization are in general between about 30° and100° C. The polymerization can be carried out in the homogeneous phase,for example in the absence of a solvent or in solution, or in theheterogeneous phase, i.e. by precipitation polymerization, emulsionpolymerization or suspension polymerization. Polymerization in solutionis preferred. Suitable solvents are, for example, toluene,N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile,tetrahydrofuran and dioxane.

Some or all of the polymers according to the invention can be complexedwith iridium(I) salts. The invention furthermore relates to polymerswherein at least some of the structural elements of the formula VII arecomplexed with iridium(I) and correspond to the formula IX or X##STR18## in which R¹ is C₁ -C₄ -alkyl, phenyl or benzyl, R³ is H or--CH₃, R⁴ and R⁵ are each H or together form a bond, X.sup.⊕ is theanion of a monobasic inorganic or organic acid and Y is an open-chain orcyclic diene having 6 to 10 C atoms, whose diene groups are bonded via 1or 2 C atoms. The preferences stated above apply to R¹ to R⁵, X.sup.⊕and Y and to the polymers. Preferably, at least 50, in particular atleast 90, mol % of the structural elements of the formula VII which arepresent are complexed.

The complexed polymers can be prepared if

(A)

(a) 0.005 to 100 mol % of at least one monomer of the formula VI or VIa,with or without a monomer of the formula I, and

(b) 0 to 99.995 mol % of at least one olefinic comonomer which differsfrom component (a) are polymerized, or

(B) a homopolymer or copolymer according to the invention, havingstructural elements of the formula VII, is reacted in solution with[(acetonitrile)₂ (Y)]IrX or withdi-[μ-chlorotetrakis(cyclooctene)-diiridium(I)]Cl and a diene Y, X beingthe anion of a monobasic inorganic or organic acid.

Process (A) is carried out essentially in the same way as thepolymerization for the preparation of the noncomplexed polymersaccording to the invention. Process (B) is carried out essentially inthe same way as the preparation of the complexes of the formula VI orVIa.

The iridium complexes according to the invention and complexed polymersare suitable as homogeneous or heterogeneous enantioselective catalystsfor the hydrogenation of unsaturated organic compounds which preferablyhave at least one prochiral C atom. In particular, they are suitable ascatalysts for transfer hydrogenation, preferably of ketones.

The invention furthermore relates to the use of iridium complexes of theformulae VI and VIa as homogeneous enantioselective catalysts for thetransfer hydrogenation of prochiral ketones with secondary alcohols, andthe use of complexed polymers according to the invention as homogeneousor heterogeneous enantioselective catalysts for the transferhydrogenation of prochiral ketones with secondary alcohols. Aparticularly suitable secondary alcohol is isopropanol. The reaction isadvantageously carried out in the absence of oxygen and at elevatedtemperature (for example 50°-150° C.). The secondary alcohol used isadvantageously employed as a solvent. The catalyst concentration ispreferably 10⁻¹ to 10⁻⁵ mol/l, relative to the reaction volume. Thereaction is preferably carried out in the presence of a base, inparticular NaOH.

The polymerizable compounds of the formula I and their polymers arevaluable optically active ligands for the preparation of chiral,homogeneous and heterogeneous catalysts with various complex-formingmetal compounds. Surprisingly, the monomeric metal complexes can bepolymerized. A particular advantage of the heterogeneous, polymericcatalysts is that they can be readily removed from the reaction mixtureand reused. As catalysts, the monomeric metal complexes have goodselectivity (optical yield) and high yields, which are even surpassed bythe heterogeneous polymeric catalysts. The examples below illustrate theinvention in more detail.

(A) PREPARATION OF STARTING MATERIALS EXAMPLE (A)

(2R, 4S, 5S)-(+)-5-amino-2-(4-vinylphenyl)-4-phenyl-1,3-dioxane

5.9 g (0.021 mol) of phosphorus pentoxide are added at 5° C. to astirred mixture of 6 g (0.024 mol) of(+)-2-amino-1-phenyl-1,3-propanediol hydrobromide, 25 ml ofp-styrylaldehyde and a pinch of 2,6-di-tert-butyl-p-cresol. Thesuspension is kept at 20° C. by cooling with ice and is stirred for 6hours. Thereafter, 20 ml of concentrated potassium carbonate solutionare added at 0° C., and a layer of 50 ml of ethyl acetate is introducedon top. The mixture is stirred vigorously with the addition of 50 ml ofice water, after which the mixture is freed from the solid constituentsby filtration. The aqueous phase is separated off and washed twice withethyl acetate. The combined organic phases are washed with concentratedsodium chloride solution (brine), dried over sodium sulfate andsubstantially freed from the solvent under about 2 kPa.

The residue is suspended in 250 ml of methanol, and 20 ml of aceticacid, a pinch of 2,6-di-tert-butyl-p-cresol and 42.3 g ofacethydrazide-trimethylammonium chloride (Girard reagent T) are added.After stirring for 15 hours at room temperature, the reaction mixture ispoured onto 1.5 l of ice water. 33.3 g of sodium carbonate are added inportions, and the product is then extracted four times with about 200 mlof ethyl acetate. After the solution has been dried over sodium sulfate,it is freed from the solvent under 1.5 kPa. The yellow oil which remainsis purified by chromatographing it over silica gel (mobile phase:methanol). 3.9 g (57% of theory) of an oily product are obtained.

[α]_(D) ²⁰ =+35.7° (c=1.143, chloroform).

250 MHz-¹ HFT-NMR (CDCl₃): δ=1.55 (s; 2H), 2.95 (m; 1H), 4.31 (m; 2H),5.13 (m; 1H), 5.27 (m; 1H), 5.72 (s; 1H), 5.76 (m; 1H), 6.74 (m; 1H),7.24-7.61 (m; 9H)ppm.

EXAMPLE (B)

(R), (S)-1-[4-(2-bromoethyl)-phenyl]-2-phenylethylamine hydrochloride

A solution of 50 g (0.66 mol) of ammonium acetate in 200 ml of methanol,2.7 g (0.43 mol) of sodium cyanoborohydride and about 100 mg of4-tert-butylpyrocatechol are added to a solution of 20 g (0.066 mol) of4-(2-bromoethyl)-phenyl benzyl ketone in 100 ml of dioxane. After themixture has been stirred for 48 hours at room temperature, it isacidified with 50 ml of concentrated hydrochloric acid (pH 2).Thereafter, methanol and dioxane are substantially distilled off underabout 2 kPa and are replaced by ethyl acetate. The solution is washedwith twice 100 ml of water and evaporated down under about 2 kPa. Theresidue is taken up with ethanol/diethyl ether (1:1). The whiteprecipitate formed is filtered off, and the filtrate is evaporated downto give an oil. After the addition of 50 ml of ethyl acetate, theproduct begins to crystallize. It is filtered off under suction anddried. Yield: 10.8 g (48% of theory) of white crystals. Melting point:165°-168° C./decomposition.

Elemental analysis: Found: C 56.49; H 5.31; N 4.29; Br 23.02%.Calculated for C₁₆ H₁₉ NBrCl (340.69): C 56.44; H 5.62; N 4.11; Br23.45%.

(R), (S)-1-(4-vinylphenyl)-2-phenylethylamine hydrochloride

A sodium alcoholate solution is prepared from 14.7 g (0.634 mol) ofsodium and 480 ml of ethanol. 65 g (0.191 mol) of (R),(S)-1-[4-(2-bromoethyl)-phenyl]-2-phenylethylamine hydrochloride areadded. The yellow suspension is heated under reflux for 15 minutes and,after cooling, is poured onto 1 l of ice water. The product is extractedwith three times 500 ml of diethyl ether. The ether phase is dried withsodium sulfate, and hydrogen chloride gas is added. After the ether hasbeen distilled off, the crude product is recrystallized from ethanoldiethyl ether (1:1). Yield: 32.2 g (65% of theory) of white crystals.

Melting point: 268°-271° C./decomposition.

Elemental analysis: Found: C 70.96; H 7.27; N 5.40; Cl 12.96; H₂ O3.78%. Calculated for C₁₆ H₁₈ NCl: 0.57 H₂ O; C 71.78%; H 7.14; N 5.19;Cl 13.13; H₂ O 3.78%.

Bis-(S)-1-(4-vinylphenyl)-2-phenylethylamine L-tartrate

From (R), (S)-1-(4-vinylphenyl)-2-phenylethylamine hydrochloride, thefree base is obtained by treatment with an ion exchanger (Amberlyst A26, OH form, mobile phase: methanol). 23.1 g (0.103 mol) of the freebase are dissolved in 500 ml of ethyl acetate, and 7.75 g (0.0502 mol)of L-(+)-tartaric acid, dissolved in 40 ml of ethanol, are added. After48 hours at about -15° C., 25 g of a crystalline product are obtained;[α]_(D) ²⁰ =+17.7° (MeOH, c=0.926). This is recrystallized six timesfrom ethanol, the optical rotation increasing to the value [α]_(D) ²⁰=+134.5° (MeOH, c=1.006).

Yield: 3.8 g

Elemental analysis: Found: C 71.50; H 6.76; N 4.97; O 16.43%; Calculatedfor C₃₆ H₄₂ O₆ N₂ : C 72.22; H 7.07; N 4.68; O 16.03%.

(S)-1-(4-vinylphenyl)-2-phenylethylamine

2.87 g (0.0048 mol) of the tartrate described above are dissolved in 50ml of ethyl acetate. 50 ml of concentrated sodium hydroxide solution areadded. The ethyl acetate phase is separated off, and the aqueous phaseis further extracted with twice 25 ml of ethyl acetate. The combinedorganic phases are washed with 25 ml of brine and dried over sodiumsulfate, a pinch of di-tert-butyl-p-cresol is added and the mixture isevaporated down under about 2 kPa. The residue is distilled at 180° C.and under 9·10⁻³ Pa in a bulb tube furnace.

Yield: 2.0 g of an oil which crystallizes.

[α]_(D) ²⁰ =+30.4° (chloroform, c=1.466).

Elemental analysis: Found: C 85.66, H 7.66; N 6.16%.

Calculated for C₁₆ H₁₇ N: C 86.06; H 7.68; N 6.28%.

EXAMPLE C

(R)-1-(4-vinylphenyl)-ethylamine L-malate

37.4 g (0.279 mol) of L-(-)-malic acid are added to a solution of 41.06g (0.279 mol) of (R), (S)-1-(4-vinylphenyl)-ethylamine in 250 ml ofmethanol at 0° C. After 15 hours, the precipitated crystals (31.0 g) arefiltered off under suction, and the mother liquor is evaporated down invacuo until crystallization begins again. A further 15 g of product areobtained. The crystal fractions are combined and recrystallized twice,in each case from 250 ml of methanol, with the addition of about 50 mgof di-tert-butyl-p-cresol.

Yield: 15.2 g of white crystalline powder,

[α]_(D) ²⁰ =+2.10° (H₂ O, c=0.95).

(R)-1-(4-vinylphenyl)-ethylamine

14.0 g of the crystalline powder [(R)-1-(4-vinylphenyl)-ethylamineL-malate] are dissolved in a little water, and a layer of 100 ml ofethyl acetate is introduced on top. The mixture is rendered alkaline(pH>10) with 30% sodium hydroxide solution, and the ethyl acetate phaseis separated off. The aqueous phase is rinsed with twice 50 ml of ethylacetate. The organic phases are combined, washed with concentratedsodium chloride solution (brine), dried over sodium sulfate andevaporated down, with the addition of a pinch of di-tert-butyl-p-cresol.The residue is distilled under a high vacuum. Boiling point: 54°C./1·10⁻² Pa, yield: 7.4 g of colorless liquid

[α]_(D) ²⁰ =+36.2° (chloroform, c=0.968).

EXAMPLE D

(S)-1-(4-vinylphenyl)-ethylamine D-malate

The mother liquors obtained in the crystallizations described underExample c are combined, and substantially freed from the solvent underabout 2 kPa. Using a method analogous to that described in Example c,the amine is liberated and distilled. Similarly to Example c, the amine(18.8 g) is dissolved in 125 ml of methanol and reacted with D-(+)-malicacid (17.12 g). The crystals obtained are recrystallized twice frommethanol. Yield: 15.0 g of white crystalline powder, [α]_(D) ²⁰ =1.84°(H₂ O, c=1.25).

(S)-1-(4-vinylphenyl)-ethylamine

Analogously to Example c, 14 g of (S)-1-(4-vinylphenyl)-ethylamineL-malate are treated with sodium hydroxide. After the mixture has beenworked up, 7.5 g of a colorless liquid are obtained. Boiling point: 53°C./1·10⁻² Pa,

[α]_(D) ²⁰ =-34.9° (chloroform, c=0.986).

EXAMPLE 1N-(6-methyl-pyridine-2-carbaldehyde)-(R)-1-(4-vinylphenyl)-ethylimine##STR19##

A solution of 1.69 g (13.9 mmol) of 6-methylpyridine-2-carbaldehyde,2.05 g (13.9 mmol) of (R)-1-(4-vinylphenyl)-ethylamine and 25 ml ofethanol is heated under reflux for 1 hour. The solvent is then distilledoff under about 3 kPa, and the residue is distilled in a bulb tubefurnace at 170° C. and under 0.11 Pa. 3.3 g (88% of theory) of an oilare obtained, which crystallises at room temperature. Melting point:about 25° C.,

[α]_(D) ²⁰ =21.6° (c=1.036, chloroform).

Elemental analysis: Found: C 81.71; H 7.25; N 11.02%. Calculated for C₁₇H₁₈ N₂ (250.35): C 81.56; H 7.25; N 11.19%.

EXAMPLE 2N-(6-methylpyridine-2-carbaldehyde)-(S)-1-(4-vinylphenyl)-2-phenyl-ethylimine##STR20##

A solution of 0.54 g (4.5 mmol) of 6-methyl-pyridine-2-carbaldehyde, 1.0g (4.5 mmol) of (S)-1-(4-vinylphenyl)-2-phenyl-ethylamine and 10 ml ofbenzene is evaporated down at room temperature and under about 3 kPa. Afurther 10 ml of benzene are added in order to distill off residualwater of reaction together with benzene under about 3 kPa. The processis repeated twice more.

After the solvent has been completely removed under about 1.5 Pa, 1.5 g(97% of theory) of white crystals are obtained.

Elemental analysis: Found: C 84.55; H 6.74; N 8.32%. Calculated for C₂₃H₂₂ N₂ (326.45): C 84.62; H 6.79; N 8.58%.

EXAMPLE 3N-(Pyridine-2-carbaldehyde)-(2R,4S,5S)-5-imino-2-(4-vinylphenyl)-4-phenyl-1,3-dioxane##STR21##

A solution of 1.60 g (15.0 mmol) of pyridine-2-carbaldehyde, 4.25 g(15.1 mmol) of (2R,4S,5S)-5-amino-2-(4-vinylphenyl)-4-phenyl-1,3-dioxanein 50 ml of benzene is evaporated down at 40° C. and under about 3.5 Pa.A further 50 ml of benzene are added in order to distill off residualwater of reaction together with benzene in vacuo. The residue is takenup with 20 ml of benzene and freed from solid constituents byfiltration, and petroleum ether is added. During this process theproduct crystallizes. It is filtered off under suction and dried at 20°C./1 Pa. Crude yield: 3.8 g of a beige powder (66% of theory). 2.3 g ofwhite crystals are obtained after crystallization from 15 ml of ethanol.Melting point 113°-114° C.,

[α]_(D) ²⁰ =+196.0° (c=1.108, chloroform).

Elemental analysis Found: C 77.10; H 6.13; N 7.20; O 9.09%. Calculatedfor C₂₄ H₂₂ N₂ O₂ (370.45): C 77.81; H 5.99; N 7.56; O 8.64%.

EXAMPLE 42-{N-[(R)-1-(4-vinylphenyl)-ethyl]-aminomethyl}-6-methylpyridine##STR22##

A solution of 1 g ofN-(6-methyl-pyridine-2-carbaldehyde)-(R)-1-(4-vinylphenyl)-ethylimine(Example 1) and 5 ml of dry tetrahydrofuran is added dropwise to amixture of 5 ml of dry tetrahydrofuran and 0.42 g of lithium alanate at0° C. and in the absence of moisture. The mixture is then stirred for 4hours without cooling, after which it is hydrolysed at 0° C. with 1 mlof concentrated sodium sulfate solution. The precipitate is filtered offand washed with ethyl acetate. The aqueous phase of the filtrate isseparated off and rinsed with ethyl acetate, and the combined organicphases are dried over sodium sulfate. After the solvent has beenevaporated off at room temperature and under about 1.5 Pa, the residueis distilled in a bulb tube furnace at a furnace temperature of 250° C.and under 0.01 Pa. 0.63 g (63% of theory) of a yellow oil is obtained.

[α]_(D) ²⁰ =+52.9 (0.926, chloroform).

250 MHz-¹ HFT-NMR (CDCl₃): δ=1.41 (d; 3H), 2.26 (broad; 1H), 2.53 (s;3H), 3.70 (s; 2H), 3.82 (q; 1H), 5.21 (m; 1H), 5.72 (m; 1H), 6.71 (m;1H), 6.97-7.50 (m; 7H)ppm.

EXAMPLE 52-{[N-[(S)-1-(4-vinylphenyl)-2-phenyl-ethyl]-aminomethyl}-6-methyl-pyridine##STR23##

1.15 g ofN-(6-methyl-pyridine-2-carbaldehyde)-(S)-1-(4-vinylphenyl)-2-phenyl-ethylimineare reduced with 0.2 g of lithium alanate similarly to Example 4. 0.9 g(83% of theory) of a colorless oil is obtained, which is chromatographedover silica gel (mobile phase: ethyl acetate). After the second fraction(main fraction) has been evaporated down and the remaining oil dried invacuo (about 1.2 Pa), 0.6 g of product is obtained as a colorless oil.

[α]_(D) ²⁰ =-15.4° (c=1.414, chloroform).

Elemental analysis Found: C 84.21 H 7.20 N 9.03%. Calculated for C₂₃ H₂₄N₂ (328.46): C 84.11; H 7.37; N 8.53%.

EXAMPLE 62-{N-[(2R,4S,5S)-2-(4-vinylphenyl)-4-phenyl-1,3-dioxan-5-yl]-aminomethyl}-pyridine##STR24##

1.0 g ofN-(pyridine-2-carbaldehyde)-(2R,4S,5S)-5-imino-2-(4-vinylphenyl)-4-phenyl-1,3-dioxane(Example 3) is reduced with 0.16 g of lithium alanate similarly toExample 4. After chromatography over silica gel (mobile phase: ethylacetate), 0.55 g of a yellowish oil is obtained.

[α]_(D) ²⁰ =+58.1 (c=1.080, chloroform).

250 MHz-¹ HFT-NMR (CDCl₃): δ=2.28 (broad; 1H), 2.71 (d; 1H), 3.68-3.93(m; 2H), 4.10-4.49 (m; 2H), 5.12 (d; 1H), 5.26 (m; 1H), 5.74 (s; 1H),5.77 (m; 1H), 6.72 (m; 1H), 6.76-8.35 (m; 13H).

EXAMPLE 7 [Ir(N,N)(HD)Cl],N,N: Compound according to Example 1

Under argon protective gas, 0.600 g (0.68 mmol) ofdi-μ-chlorotetrakis(cyclooctene)diiridium(I) is dissolved in 50 ml ofbenzene. 4.4 ml of 1,5-hexadiene (HD) are added at 10° C. The mixture isstirred for 30 minutes at room temperature, after which 375 mg (1.5mmol) ofN-(6-methylpyridine-2-carbaldehyde)-(R)-1-(4-vinylphenyl)-ethylimine(Example 1) are added.

After the mixture has been stirred for 1 hour at room temperature, 100ml of n-hexane are added in the absence of air. The product crystallizesout in the course of 2 hours at 0° C. Under an argon atmosphere, it isfiltered off under suction, washed with n-hexane and dried for 3 hoursunder 1.3 Pa. Yield: 0.500 g (66% of theory) of a beige powder.

Elemental analysis: Found: C 48.05; H 5.16; N 4.99; Ir 34.3%. Calculatedfor C₂₃ H₂₈ N₂ IrCl (560.16): C 49.32; H 5.04; N 5.00; Ir 34.31%.

EXAMPLE 8 [Ir(N,N)(HD)I], N,N: Compound according to Example 3

0.492 g (0.55 mmol) of di-μ-chlorotetrakis(cyclooctene)diiridium(I) isdissolved in 80 ml of acetone under argon protective gas. 3.4 ml of1,5-hexadiene (HD) are added at 5° C. The mixture is heated to 35° C.for 10 minutes, after which a solution of 0.380 g (2.5 mmol) of sodiumiodide in 12 ml of water is added at 0° C. in the absence of air,followed immediately by a solution ofN-(pyridine-2-carbaldehyde)-(2R,4S,5S)-5-imino-2-(4-vinylphenyl)-4-phenyl-1,3-dioxane(Example 3) in 4 ml of acetone. After 1 hour, the mixture is evaporateddown to half its volume. In the course of one hour, the productcrystallizes out at 0° C. It is filtered off under suction underprotective gas, washed with about 40 ml of water and dried overphosphorus pentoxide for 8 hours under 0.13 Pa. Yield: 0.520 g (67% oftheory) of dark blue crystals.

Elemental analysis: Found: C 46.59; H 4.16; N 3.60; I 16.31. Calculatedfor C₃₀ H₃₂ N₂ O₂ Ir (771.71); C 46.69; H 4.18, N 3.63; I 16.44%.

EXAMPLE 9 [Ir(N,N)(COD)]BF₄, N,N: Compound according to Example 4, COD:cycloocta-1,5-diene

0.469 g (1.0 mmol) of [bis(acetonitrile)cycloocta-1,5-diene]iridiumtetrafluoborate is dissolved in 15 ml of dichloromethane under argonprotective gas. A solution of 5 ml of dichloromethane and 0.252 g (1.0mmol) of2-{N-[(R)-1-(4-vinylphenyl)-ethyl]-aminomethyl}-6-methyl-pyridine(Example 4) is added dropwise at room temperature and while stirring.After 1 hour, the mixture is evaporated down under about 600 Pa to aboutone third of its volume. 60 ml of diethyl ether are added, the productseparating out as a solid precipitate in the course of 2 hours. Theproduct is filtered off under suction under an argon atmosphere, washedthree times with diethyl ether and dried for 15 hours under 0.1 Pa.Yield: 0.588 g (92% of theory) of ochre yellow crystals.

Elemental analysis: Found: C 45.07; H 5.12; N 4.27; Ir 28.5%. Calculatedfor C₂₅ H₃₂ N₂ IrBF₄ ·1.5 H₂ O (666.57): C 45.05; H 5.29; N 4.20; Ir28.83%.

EXAMPLE 10 [Ir(N,N)(COD)]BF₄,N,N: Compound according to Example 5

0.469 g (1.0 mmol) of [bis(acetonitrile)cycloocta-1,5-diene]iridiumtetrafluoborate is reacted with 0.316 g (1.0 mmol) of2-{N-[(S)-1-(4-vinylphenyl)-2-phenyl-ethyl]-aminomethyl}-6-methylpyridine(Example 5) analogously to Example 9. After working up in acorresponding manner, 0.641 g (91% of theory) of yellow crystals areobtained.

Elemental analysis: Found: C 49.80; H 5.19; N 3.82; Ir 24.9%; F 10.32%.Calculated for C₃₁ H₃₆ N₂ IrBF₄ ·2 H₂ O (751.68): C 49.53; H 5.36; N3.79; Ir 25.57%; F 10.11%.

EXAMPLE 11 [Ir(N,N)(COD)BF₄,N,N: Compound according to Example 6

0.260 g (0.605 mmol) of [bis(acetonitrile)cycloocta-1,5-diene]iridiumtetrafluoborate is reacted with 0.225 g (0.605 mmol) of2-{N-[(2R,4S,5S)-2-(4-vinylphenyl)-4-phenyl-1,3-dioxan-5-yl]aminomethyl}-pyridine(Example 6) analogously to Example 9. After working up in acorresponding manner, 0.380 g (79% of theory) of orange brown crystalsare obtained.

Elemental analysis: Found: C 48.36; H 4.93; N 3.74; F 10.18; Ir 24.5%.Calculated for C₃₂ H₄₀ N₂ O₄ IrBF₄ ·2 H₂ O (795.69): C 48.30; H 5.07; N3.52; F 9.55; Ir 24.16%.

EXAMPLE 12 Copolymer of [Ir(N,N)(HD)Cl] according to Example 7 (2 mol%), 2-ethylhexyl methacrylate (96 mol %) and technical-gradedivinylbenzene (2 mol %)

30.0 mg (0.0536 mmol) of the complex, prepared according to Example 7,6.97 mg (0.0536 mmol) of technicalgrade divinylbenzene (techn. DVB) and509.8 mg (2.571 mmol) of freshly distilled 2-ethylhexyl methacrylate aredissolved in 7 ml of tetrahydrofuran. The dark reddish brown solution ismixed with 3.3 mg of azobisisobutyronitrile (AIBN), dissolved in 1 ml oftetrahydrofuran, in an ampoule flushed with argon. The mixture is heatedto 70° C. in the absence of air, and the same amount of AIBN is addedafter 24 hours and then after a further 18 hours. After polymerizationhas continued for a further 30 hours at 75° C., a finely dividedemulsion which is fluorescent red in transmitted light is obtained. Theresidual content of 2-ethylhexyl methacrylate monomer is determined bymeans of gas chromatography (CW-20M) as 7% of the amount originallyused.

The volume is evaporated down to 3.5 ml, and the emulsion is used forcatalysis. The catalyst capacity is determined as 1.148·10⁻⁵ mol ofrepeating units of iridium complex per 1 ml of emulsion.

EXAMPLE 13 Copolymer of N,N-ligand (according to Example 1, 5 mol %) andstyrene (95 mol %)

0.2504 g (1 mmol) ofN-(6-methyl-pyridine-2-carbaldehyde)-(R)-1-vinylphenyl)-ethylimine(N,N-ligand) and 1.979 g (19.0 mmol) of freshly distilled styrene aredissolved in 5 ml of benzene. In an ampoule flushed with argon, thesolution is mixed with 24.6 mg of AIBN and heated for 20 hours at 70° C.The viscous solution formed is diluted with about 1/3 of its volume ofbenzene. By pouring the mixture into 250 ml of methanol, a white powderis obtained. It is dissolved in tetrahydrofuran and reprecipitated frommethanol. It is separated off from the supernatant precipitating agentby centrifuging, and dried for 15 hours at 40° C. and under 0.12 Pa.Yield: 1.03 g, [α]_(D) ²³ =+0.44° (c=4.966, chloroform).

Elemental analysis: Found: C 90.43; H 7.70; N 1.39%. Calculated for0.056 (C₁₇ H₁₈ N₂)+0.944 (C₈ H₈): C 90.92; H 7.68; N 1.40%.

Ligand capacity: 0.499 mmol/g.

EXAMPLE 14 Copolymer of [Ir(N,N)(HD)Cl] (5 mol %) and styrene (95 mol %)by polymer-analogous reaction at the polymer ligand according to Example13

0.0893 g of di-μ-chlorotetrakis(cyclooctene)diiridium(I) BF₄ isdissolved in 5 ml of benzene under argon protective gas. 1.2 ml of1,5-hexadiene (HD) are added at 10° C. The mixture is stirred for 30minutes at room temperature, after which a solution of 0.4000 g ofpolymer, prepared according to Example 13, and 5 ml of benzene is addeddropwise. A dark red solution is formed, which, after it has beenstirred for 1 hour in the absence of air, is evaporated down to about1/3 of its volume and used directly for the catalytic transferhydrogenation. The catalyst capacity is determined as 1.766·10⁻⁵ mol ofrepeating units per 1 ml of solution.

EXAMPLE 15 Copolymer of [Ir(N,N(COD)BF₄ (according to Example 9) (2 mol%), 2-ethylhexyl methacrylate (96 mol %) and 1,4-divinylbenzene (2 mol%)

95.9 mg (0.15 mmol) of the complex, prepared according to Example 9,19.5 mg (0.15 mmol) of 1,4-divinylbenzene (1,4-DVB) and 1.428 g (7.2mmol) of freshly distilled 2-ethylhexyl methacrylate are dissolved in 12ml of tetrahydrofuran. The ochre solution is mixed with 9.23 mg of AIBN,dissolved in 0.2 ml of tetrahydrofuran, in an ampoule flushed withargon. The mixture is heated to 70° C. in the absence of air, and thesame amount of AIBN is added again after 65 hours. After a further 48hours at 70° C., a viscous, finely divided emulsion having a palereddish brown color is obtained. The volume is brought to 10 ml, and thecatalyst capacity is determined as 1.42·10⁻⁵ mol of repeating units ofiridium complex per 1 ml of emulsion.

EXAMPLE 16 Copolymer of [Ir(N,N)(COD)BF₄ (according to Example 10)] (2mol %), 2-ethylhexyl methacrylate (96 mol %) and 1.4-DVB (2 mol %)

107.3 mg (0.15 mmol) of the complex, prepared according to Example 10,19.5 mg (0.15 mmol) of 1,4-DVB and 1,428 g (7.2 mmol) of 2-ethylhexylmethacrylate in 12 ml of tetrahydrofuran are copolymerized analogouslyto Example 15.

A viscous, finely divided emulsion having an ochre yellow color isobtained.

EXAMPLE 17 Copolymer of [Ir(N.N)(COD)]BF₄ (according to Example 11) (2mol %), 2-ethylhexyl methacrylate (96 mol %) and 1.4-DVB (2 mol %)

113.9 mg (0.15 mmol) of the complex, prepared according to Example 11,19.5 mg (0.15 mmol) of 1,4-DVB and 1.428 g (7.2 mmol) of 2-ethylhexylmethacrylate in 12 ml of tetrahydrofuran are copolymerized analogouslyto Example 15.

A viscous orange brown emulsion is obtained. The concentration isadjusted as described in Example 15.

EXAMPLE 18 Copolymer of N,N-ligand (according to Example 3) (2 mol %),2-ethylhexyl methacrylate (96 mol %) and 1,4-DVB (2 mol %)

111.1 mg (0.3 mmol) ofN-(pyridine-2-carbaldehyde)-(2R,4S,5S)-5-imino-2-(4-vinylphenyl)-4-phenyl-1,3-dioxane,39.1 mg (0.3 mmol) of 1,4-DVB and 2.856 g (0.0144 mol) of 2-ethylhexylmethacrylate in 15 ml of tetrahydrofuran are copolymerized analogouslyto Example 13. After 22 hours, a colorless oil is obtained which isswelled by adding benzene and evaporating off tetrahydrofuran underabout 3 kPa, the procedure being carried out twice. The product is usedfor the further reaction, without isolation (Example 19).

EXAMPLE 19 Copolymer of [Ir(N,N)(HD)Cl] (2 mol %), 2-ethylhexylmethacrylate (96 mol %) and 1,4-DVB (2 mol %) obtained bypolymer-analogous reaction at the polymer ligands according to Example18

0.130 g of di-μ-chlorotetrakis(cyclooctene)diiridium (I) is reacted with1,5-hexadiene and the polymer according to Example 18, analogously toExample 3. After 16 hours, a deep blue gel, which is reddish violet intransmitted light, is obtained. It is swelled by adding isopropanol inthe absence of air and evaporating off the solvent, this procedure beingcarried out three times. A brown gel is obtained, and is used directlyfor catalysis. A sample is dried for 15 seconds under 0.1 Pa.

Elemental analysis: Found: C 71.48; H 10.73; N 0.3; Ir 1.71%. Calculatedfor 0.02 (C₃₀ H₃₂ N₂ O₂ IrCl)+0.02 (C₁₀ H₁₀)+0.96 (C₁₂ H₂₂ O₂) C 71.63;H 10.72; N 0.27; Ir 1.86%.

EXAMPLE 20 Copolymer of [Ir(N,N)(COD)]BF₄ according to Example 9 (2 mol%), tert-butyl methacrylate (96 mol %) and 1,4-divinylbenzene (2 mol %)

128 mg (0.2 mmol) of the complex prepared according to Example 9, 26 mg(0.2 mmol) of 1,4-DVB and 1.365 g (9.6 mmol) of tert-butyl methacrylatein 12 ml of tetrahydrofuran are copolymerized analogously to Example 15.

A viscous, finely divided emulsion having an orange brown color isobtained. The volume is adjusted to 10 ml.

(C) USE EXAMPLES EXAMPLE 21

70.0 mg of the complex prepared according to Example 7 are dissolved in31 ml of isopropanol in the absence of oxygen (argon atmosphere). Thesolution is stirred for one hour at 60° C., after which 5.0 ml of 0.1normal sodium hydroxide solution are added. Stirring is continued for afurther hour at 60° C., after which a solution of 31 ml of isopropanoland 1.85 g of 1-phenylbutanone is added in the absence of oxygen. Themolar ratio of substrate to catalyst [S]/[cat.] is thus 100, and thecatalyst concentration [cat.] is 2·10⁻³ mol/l.

After 16 hours at 60° C., the yield of 1-phenylbutanol determined by gaschromatography (10% CW-20M, 185° C., isothermal) is 81.1%.

To determine the enantiomer content according to Mosher (J. A. DALE, D.L. DULL and H. S. MOSHER, J. Org. Chem. 34 (1969) 2543), a sample (about0.5 ml) is substantially freed from the solvent, and 50 μl of opticallypure α-methoxy-α-trifluoromethylphenylacetyl chloride and 0.25 ml of drypyridine are added at 0° C. After 15 minutes, the mixture is heated at70° C. for 30 minutes and, after cooling, 3 ml of 10% citric acidsolution are added, and the diastereomeric esters are extracted withdiethyl ether.

An enantiomeric excess of (R)-1-phenylbutanol of ee=26.0% is determinedby gas chromatography (capillary column CW 20, 190° C., isothermal).

EXAMPLE 22

The complex according to Example 8 is used for the catalyticenantioselective transfer hydrogenation of 1-phenylbutanone similarly toExample 21.

After 19 hours 30 minutes, the yield of 1-phenylbutanol is 23.6% and theenantiomeric excess ee=60.3% of (S).

EXAMPLE 23

The complex according to Example 9 is used for the catalytic,enantioselective transfer hydrogenation of 1-phenylbutanone similarly toExample 21.

After 2 hours 50 minutes, the yield of 1-phenylbutanol is 97.3%, and theenantiomeric excess ee=48.7% of (R).

EXAMPLE 24

The complex according to Example 11 is used for the catalytic,enantioselective transfer hydrogenation of 1-phenylbutanone similarly toExample 21.

After 20 hours, the yield of 1-phenylbutanol is 75.2%, and theenantiomeric excess ee=58.1% of (S).

EXAMPLE 25

3.5 ml of the emulsion obtained according to Example 12 are added to 15ml of isopropanol in the absence of oxygen (argon atmosphere). After themixture has been stirred for 1 hour at 60° C., 1.61 ml of 0.1 normalsodium hydroxide solution are added, the previously finely dispersedpolymer agglomerating to form larger particles. Stirring is continuedfor a further hour at 60° C., after which a solution of 5 ml ofisopropanol and 0.60 g of 1-phenylbutanone is added in the absence ofoxygen. The molar ratio of substrate to catalyst is thus [S]/[cat.]=100.

After 19 hours at 60° C., the yield of 1-phenylbutanol is determined as79.7% by gas chromatography (10% CW-20M, 185° C., isothermal).

To determine the enantiomer content according to Mosher, a sample (about0.5 ml) is substantially freed from the solvent, and 50 μl of opticallypure α-methoxy-α-trifluoromethylphenylacetyl chloride and 0.25 ml of drypyridine are added at 0° C. After 15 minutes, the mixture is heated at70° C. for 30 minutes and, after cooling, 3 ml of 10% citric acidsolution are added, and the diastereomeric esters are extracted withdiethyl ether.

An enantiomeric excess of (R)-1-phenylbutanol of ee=66.2% of (R) isdetermined by gas chromatography (capillary column CW 20, 190° C.,isothermal).

EXAMPLE 26 5.5 ml of the solution obtained according to Example 14 areused for the catalytic enantioselective transfer hydrogenation of1-phenylbutanone, similarly to Example 25. Under the reaction conditionsfor activation, the catalyst agglomerates to form a compact mass.

After 41 hours, the yield of 1-phenylbutanol is 12.4%, and theenantiomeric excess ee is 42.2% of (R).

EXAMPLE 27

0.8 ml of the emulsion obtained according to Example 15 is used for thecatalytic, enantioselective transfer hydrogenation of 1-phenylbutanone,similarly to Example 25. However, the concentration ratio[S]/[cat.]=1000 is chosen. The heterogeneous catalyst is finelydispersed during the reaction.

After 6 hours, the yield of 1-phenylbutanol is 91.9%, and theenantiomeric excess ee=85.3% of (R).

EXAMPLE 28

70 ml of the emulsion obtained according to Example 15 are used for thecatalytic, enantioselective transfer hydrogenation of 1-phenylbutanone,similarly to Example 25. The concentration ratio [S]/[cat.]=100 ischosen.

After 2 hours 50 minutes, the yield of 1-phenylbutanol is 96.1%, and theenantiomeric excess ee=78.7% of (R).

EXAMPLE 29

The catalyst used according to Example 28 is recovered by separating itoff from the supernatant solution, and the residual brown gel is washedtwice with isopropanol in the absence of air. After decantation, the gelis dispersed with 30 ml of isopropanol, and 3.98 ml of 0.1 normal sodiumhydroxide solution are added at 60° C. After 1 hour at 60° C., 1.48 g of1-phenylbutanone and 30 ml of isopropanol are added. The procedure iscontinued as described in Example 25.

After 2 hours, the yield of 1-phenylbutanol is 94.5%, and theenantiomeric excess ee=82.6% of (R).

The processes of recovery, purification and reuse of the catalyst arerepeated twice more.

The yields of 1-phenylbutanol are 94.6% after 3 hours 25 minutes and90.9% after 3 hours 45 minutes, and the enantiomeric excesses areee=80.8% of (R) and ee=78.8% of (R), respectively.

EXAMPLE 30

2.2 ml of the emulsion obtained according to Example 15 are used for thecatalystic, enantioselective transfer hydrogenation of1,4-diphenylbutanone similarly to Example 25.

After 6 hours 30 minutes, the yield of 1,4-diphenylbutanol is 94.5%. Theenantiomeric excess is determined, by the Mosher method, as ee=85.7%from the ¹⁹ F-NMR spectrum of the diastereomeric esters.

EXAMPLE 31

7.0 ml of the emulsion obtained according to Example 17 are used for thecatalytic, enantioselective transfer hydrogenation of 1-phenylbutanone,analogously to Example 25. The heterogeneous catalyst is coarselydispersed during the reaction.

After 20 hours, the yield of 1-phenylbutanol is 85.8%, and theenantiomeric excess ee=78.7% of (S).

EXAMPLE 32

5 ml of the emulsion obtained according to Example 20 are used for thecatalytic enantioselective transfer hydrogenation of 1-phenylbutanone,similarly to Example 25. The concentration ratio [S]/[cat.]=100 ischosen. After the end of the activation time, the reaction temperatureis reduced to 24° C.

After 45 hours, the yield of 1-phenylbutanol is 95.2%, and theenantiomeric excess ee=90.6% of (R).

I claim:
 1. An optically active compound of the formula ##STR25## inwhich R² is a radical of the formula II or IIa ##STR26## in which R³ isH or --CH₃, and * represents predominantly R or predominantly Sconfiguration.
 2. A pure stereoisomeric optically active amine of theformula V ##STR27## in which the chiral *C atoms in formula V have the2R, -4S, 5S configuration.